Disazo dyestuffs containing the {60 :{62 -dichloro- or {60 :{62 -dibromopropionylamino group

ABSTRACT

Fibre-reactive disazo dyestuffs containing at least two and at most four sulphonic acid groups and at least one and at most two aromatically bound Alpha : Beta -dichloro- or Alpha : Beta dibromopropionylamino groups correspond to the formula   WHEREIN R is an o-sulfobenzene radical which may be further substituted by lower alkyl, lower alkoxy, trifluoromethyl, chlorine or bromine, one X is hydrogen and the other X is a sulfonic acid group and R2 is a benzene radical which may be substituted by lower alkyl, lower alkoxy, trifluoromethyl, chlorine, bromine, sulfo or nitro. These dyestuffs yield brilliant dyeings of excellent general fastness-properties on cotton.

United States Patent de Montmollin et a1.

Dec. 2, 1975 DISAZO DYESTUFFS CONTAINING THE azB-DICHLORO- ORa:B-DIBROMOPROPIONYLAMINO GROUP Inventors: Rene de Montmollin, Riehen;Henri Riat, Arlesheim, both of Switzerland Assignee: Ciba-Geigy AG,Basle, Switzerland Filed: June 1, 1972 Appl. No.: 258,773

Related US. Application Data Division of Ser. No. 876,069, Nov. 12,1969, Pat. No. 3,755,290, which is a continuation-in-part of Ser. No.753,829, July 22, 1968, abandoned, which is a continuation of Ser. No.608,710, Nov. 1, 1966, abandoned, which is a division of Ser. No.305,539, Aug. 29, 1963, abandoned, which is a continuation-in-part ofSer. No. 731,097, April 28, 1958, abandoned.

US. Cl. 260/174; 260/178; 260/181; 260/184; 260/185; 260/187; 260/191Int. CL. C09B 62/00; CO9B 62/04; D06P 3/66 Field of Search 260/181, 185,189, 191, 260/174, 178, 184, 187

References Cited UNITED STATES PATENTS 2/1948 Knight et al. 260/1856/1962 Riat et al. 260/196 2/1964 l-lurbin et al 260/199 3/1964 Bruggeret al. 260/151 3/1964 Bossard et al. 260/151 12/1965 Lange 260/1633/1970 De Montmollin et al. 260/181 FOREIGN PATENTS OR APPLICATIONS885,815 12/1961 United Kingdom 260/199 Primary Examiner-Floyd D. HigelAttorney, Agent, or Firm-Wenderoth, Lind & Ponack [57] ABSTRACTFibre-reactive disazo dyestuffs containing at least two and at most foursulphonic acid groups and at least one and at most two aromaticallybound a:B-dichloroor azB-dibromopropionylamino groups correspond to theformula 5 Claims, No Drawings DISAZO DYESTUFFS CONTAINING THEazB-DICHLORO- OR azB-DIBROMOPROPIONYLAMINO GROUP CROSS-REFERENCES TORELATED APPLICATIONS This is a division of application Ser. No. 876,069,filed Nov. 12, 1969, and now U.S. Pat. No. 3,755,290, which applicationis a continuation-in-part application of our copending application Ser.No. 753,829, filed July 22, 1968, now abandoned which was a streamlinedcontinuation of our application Ser. No. 608,710, filed Nov. 1, 1966,now abandoned, which itself was a division of our application Ser. No.305,539, filed Aug. 29, 1963, now abandoned, which in turn was acontinuation-in-part of our application Ser. No. 731,097, filed Apr. 28,195 8, now abandoned.

This invention provides valuable new water-soluble azo dyestuffs whichcontain at least one aromatically bound :,B-dichloroordibromopropionylamino group. More especially it provideso-sulfobenzene-o-hydroxy or -o-aminomonoazo naphthalene dyestuffscontaining at least two and at most three sulfonic acid groups and atleast one and at most two aromatically bound azB- dichloroordibromopropionylamino groups, which dyestuffs may be further substitutedin the benzene radical by lower alkyl, lower alkoxy, phenoxy,acetylamino, chlorine or bromine. Furthermore, it also providesbenzenemonoazosulfonaphthalene dyestuffs ,containing at least two and atmost three sulfonic acid 7 groups and at least one and at most twoaromatically bound azB-dichloro or dibromo propionylamino groups, whichdyestuffs may be further substituted in the benzene radical by amino,lower alkyl or lower alkoxy. The invention also provides o-sulfobenzeneor sulfonaphthalenemonoazo pyrazolone dyestuffs contain ing at least twoand at most three sulfonic acid groups and at least one and at most twoaromatically bound azB-dichloroor -dibromopropionylamino groups, whichdyestuffs may be further substituted in the diazo component by loweralkyl, lower alkoxy, phenoxy, acylamino other thanafi-dihalogenpropionylamino, chlorine or bromine and in which dyestuffsthe coupling component is a 3-methyl or 3-carboxy-5-pyrazolone bound tothe azo-linkage in 4-position.

Included in the invention are moreover complex chromium, cobalt orcopper compounds of monoazo dyestuffs containing at least two and atmost three sulfonic acid groups and at least one and at most two aro-;matically bound azB-dichloroor -dibromopropionylamino groups, whichdyestuffs correspond to the formula v i R N=N--Rl wherein R is theradical of an o-hydroxybenzene or an o-hydroxynaphthalene which may befurther substituted by lower alkyl, lower alkoxy, acylamino other thana,B-dihalogenopropionylamino, chlorine or bromine and R is the radicalof a hydroxyor aminonaphthalene bound to the azolinkage in o-positionto'a hy- I 5 A-HNG f droxy or amino group or the radical of a 3-methylor3-carboxy-5-pyrazolone bound to the azo-linkage in 4- position. Furthercomplexes falling within this inven- 5 tion are chromium, cobaltorcopper complexes of monoazodyestuffs containing at least two and atmost three sulfonic acid groups and corresponding to the formula whereinR is an o-sulfobenzene radical which may be further substituted by loweralkyl, lower alkoxy, trifluoromethyl, chlorine orbromine, one X ishydrogen and the other X is a sulfonic acid group and R is a benzeneradical which may be substituted by lower alkyl, trifluoromethyl,chlorine or bromine, sulfo or nitro. In the above definition the termlower means: containing up to 4 carbon atoms.

Especially valuable groups of such dyestuffs are e.g.:

1. Dyestuffs of the general formula wherein A stands for a,B-dichloroordibromopropionyl, R for hydrogen or an optionally substituted loweralkyl radical, and D for the radical of a diazo component which containsat least one sulfonic acid group and which also may contain anazB-dichloroor dibromopropionylamino group.

Valuable are e.g., diazo components in which the radical D, has thefonnula SO H SO. H

SO H 01 CH Q Q H SO l 3 7 3H CH 7 O 5Q SO H CH SO H 3 803K 01 oH co-HNOS0 H SO I 3 H SO H NHCOCH=CH NH-A 2. Dyestuffs of the general formula H08 so H' OH HN-A HO D2 N-N 4o 3S 9 HO S Y Y S0 H wherein A has theaforecited meaning, one Y stands for 3 SO H hydrogen and the other for asulfonic acid group, and 3 D stands for the radical of a diazo componentwhich may contain one water-solubilizing group, e.g. H038 or orespecially diazo components mentioned above, which contain anazB-dichloroor dibromopropionylamino group and/or a sulfo group.

3. Dyestuffs of the general formula 5 and wherein the benzene nucleus Zmay contain further substituents, as e.g.

N'H-CO-CH3 wherein A and R possess the aforecited meanings D3 4. Monoazodyestuffs with at least two sulfonic acid stands for the radical of adiazo component which contains at least two sulfonic acid groups and maycontain further substituents such as azo groups, especially the radicalsgroups of the general formula ANH-D4N=NK, wherein A possesses theaforecited meaning, D stands for the radical of a diazo component, e.g.,

5. Dyestuffs of general formula SOBH 50511 O G or D .,-N=N-K,-NA

whereby the sulfonic acid group is in ortho-position to wherein A and Rpossess the aforecited meanings, D the 2120 g p and 1 Stands the radicalof a ystands for the radical of a diazo component whichcondroxynaphthalenesulfonic acid which may be further tains at least onesulfonic acid group and may contain substituted, e.g. an azo group, e.g.

OH HO OH H 9 l 9 y 5 110 s f SO H CH 3 SO H 5 HO HO SO H NH I 9 HO sm(IOCH (In I H0 8 HO NHCOCH HO E 3 m NCOCH Cl 1 H H H or a ketomethylenecompound, e.g. S0 H COOH HO S 40 5 l 01 SO H SO H 3 S0 H --CHCO S0 H I01 v I SO H 3 CH=CH NHCOCH 3 -CH-CO so H H0 s SO3H CH HO s ON=N- so H 5N SO H HOS SO H 7 and K for the radical of a coupling compound whichcouples in the adjacent position to an enolizable keto group, e.g.

i N H=CH GH-CO A I 3 SO3H SOH H058 oqu-o H038 N A H033 wherein R and Ahave the aforecited meanings, or alternatively to the diazo component,e.g.:

In addition the a,B-dichloroor dibromopropionyl radical may be attachedto both the diazo-component and the coupling-component, e.g., in thefollowing combination A-HN 0 c 0 l\l=N N-A HO 3 HO s wherein A and Rpossess the aforecited meanings.

Naturally 2:1 metal complexes as well as 121 complexes can be. produced.The former contain preferably chromium or cobalt metal atoms.

The dyestuffs of this invention may be obtained from dyestuff componentswhich already contain the dihalogenated propionyl radical. Such dyestuffcomponents are obtainable by methods in themselves known, for example,by the acylation of appropriate compounds with a halide or anhydride ofan oaB-dihalogen-propionic acid.

I Suitable compounds for this purpose are those which contain an easilyacylatable amino group, for example, a monoalkylamino group or a primaryamino group, and in the case of diazo-components, a less easilyacylatably primary amino group, and in the case of coupling componentseither a less easily acylatable amino group or a hydroxyl groupresponsible for coupling. As amino groups that are less readily acylatedthere may be mentioned principally those which occupy a position vicinalto an acid group, for example, a sulfonic acid group.Arninohydroxy-compounds are acylated in such manner that esterificationof the hydroxyl group is avoided.

Instead of introducing the aforesaid radicals into the dyestuffcomponents before the dyestuff is made, they may be introduced into thefinished dyestuffs. Thus, valuable dyestuffs containing anazB-dichloroor dibromopropionylamino group can be obtained by reacting adyestuff which contains an acylatable amino group, and above all a freeamino group, with, for example, azB-dichloroor dibromopropionic acidchloride or anhydride. I

As soluble organic dyestuffs, which can be made in the above manner,there may be used metal-free or metalliferous monoazoanddisazo-dyestuffs which latter may also be prepared by metallisation.Especially good results are obtained with soluble azodyestuffs whichpossess no affinity for cotton or at most no pronounced affinitytherefor. Such amino-azo-dyestuffs may be obtained e.g., by hydrolysisof acylamino-azodyestuffs, by reduction of the nitro groups ofnitro-azodyestuffs or by coupling a diazotized aromatic amine with acoupling component containing an acylatable amino group.

As amines which, after diazotation, may be used as diazo components toproduce monoand disazo dyestuffs for use of the process of thisinvention, there may be mentioned for example: aminobenzene, l-amino-2(3or 4)-methylbenzene, l-amino-4-methoxybenzene-2-sulfonic acid,l-aminobenzene-2(3 or 4)-sulfonic acid, l-aminobenzene-2,5(or2,4)-disulfonic acid, 3 (or 4)- nitrol -aminobenzen'e, 4-nitrol-aminobenzene-2- sulfonic acid,

4 (or 5)acetylamino-1-aminobenzene-2-sulfonic acid,

4- (or 3) acetylamino-l-aminobenzene, 4 (or 5)-nitro-2-hydroxyl-aminobenzene, 6-acetylamino-2-hydroxy-l -aminobenzene-5-sulfonic acid,2-hydroxy-l-aminobenzene-4 (or 5)-sulfonic acid, 2 (3 or 4)-aminobenzoicacid, 4-chloroacetylamino- 1 -am inobenzene-Z-sulfonic acid,

l-phenyl-3-methyl-4-[4 -(4 '-amino-2 -methyl phenyl-3-methyl]-phenylazo-5-pyrazolone-2 ,5 6"trisulfonic acid (reddishyellow),

4-amino-4'-(4'-methoxy)-phenylazo-stilbene-2,2-

disulfonic acid (orange),

l-naphthyl-(2)-3-methyl-4-[4"-(4"'-amino)-phenyl]-phenylazo-5-pyrazolone-4',8,2"-trisulfonic acid (brown-orange),

l-phenyl-3-methyl-4-[4 3 '-amino )-phenyl-azo-3 methyl-phenylazo-5-pyrazolone-2 ,4 ,6 -trisulfonic acid (orange-brown),

l-phenyl-3-methyl-4-[4 -(4 '-amino )-phenylaZo-2 methoxy-Smethyl]-phenylazo-5-pyrazolone-2 ,5 2-trisulfonic acid (orange-brownl-naphthyl-(Z )-3-methyl-4-[4 -amino)-phenylazo- 3-methyl]-phenylazo-5-pyrazolone-4 ,8 ,2 '-trisulfonic acid(orange-brown),

1-naphthyl-(2)-3-methyl-4-[4 '-(4' -amino phenylazo-3 '-methyl]-phenylazo-5 -pyrazolone-5 7 ,2 '-trisulfonic acid (orange-brown l-( 4'-amino)-stilbenyl-(4' )-3-methyl-4-(4phenylazo)-phenylazo-5-pyrazolone-2 ,2 ,2 ,4 te'trasulfonic acid(orange-brown),

l-hydroxy-2-( 4-phenylazo)-7-amino-naphthalene- 3,2,4"-trisulfonic acid(blue-red),

1-(4 '-amino'2 '-methyls ulfonylamino )-phenylazo-3- methyl-4-phenylazob enzene-2 ,4 -disulfonic acid (orange-brown),

l-( 4 '-amino-2 -sulfoace tylamino)-phenylaZo-3-methyl-4-phenylazobenzen e-2 ,4' '-disulfonic acid(orange-brown),

2-[4'-(4' '-amino)-naphthyl-( 1 )-azo] -phenylazonaphthalene-4,6,8,7-tetrasulfonic acid (orange-brown 2-[4-(4"-amino-3 "-ethoxy)-naphthyl-(1 )-azo]- phenylazonaphthalen e-4,8 ,3 '-trisulfonic (orange-brown),

i2-[4'-( 1 "-hydroxy-6 '-amino)-naphthyl-(2 )-azo-2 methyl-phenylazonaphthalene-6,8 3 '-trisulfonic acid (blue-red),

acid

naphthyl-( 1 )-azobenzene-4,7 ,3 '-trisulfonic acid 1 (blue-violet)naphthyl-( 1 ')-azo-benzene-2,4,6' '-trisulfonic acid k (red-brown),

4 (4' '-amino-2 -methyl)-phenylazo-4-( 1 "-hydroxy)- naphthyl-( 2")-azo-3 ,3 '-dimethyll l '-diphenyl- 6,6',4 "-trisulfonic acid (red),

4-( 4' -amino-3 -methoxy-6' '-methy1 )-phenylazo-4 l2,2',4'",6-tetrasulfonic acid (red),

@4-(4' -acetylamino)-phenylazo-4'-( 1 "'-hydroxy-6"'-amino)-naphthyl-(2' )-azo-1 ,1 '-diphenyl-2,2 ,3 trisulfonic acid (red),

4-(4"-amino-2' '-methyl)-phenylazo-4-( 1 "'-hydroxy)- naphthyhl-( 2)-azo-2,2 '-dimethyl- 1 l '-diphenyl- 5',3"',6"'-trisulfonic acid (red),

4-(4 -amino-2' '-sulfoacetylamino)-phenylazo-4'-( 1 'A '-hydroxy)-naphthyl-( 2' )-azo-2,2'-dimethyl-1 ,1 diphenyl-S ',4'-disulfonic acid(red),

4-(4"-amino-2"-methyl)-phenylazo-4'-( 1 '-hydroxy- 8-amino )-naphthyl-(2 )-azo-2,2 '-dimethyl-1 ,l diphenyl-S ,3 ,6' '-trisulfonic acid(red-violet),

4-(4' '-amino-2 -acetylamino)-phenylazo-4'-(2 hydroxy)-naphthyl-( l"')-azo-1 ,1 -diphenyl-5 ,3 tetrasulfonic acid (red).

The acylation of such a dyestuff containing an acylatable amino groupwith one of the aforesaid dihalogenpropionic acid halides or anhydridesis advantageously carried out in the presence of an acidbinding agentsuch as sodium acetate, sodium hydroxide or sodium hydrogen carbonateand under relatively mild conditions, for example, in an organic solventor at a relatively low temperature in an aqueous medium.

The dyestuffs of this invention are new. They are suitable for dyeing orprinting especially polyhydroxylated materials of fibrous structure suchas cellulosic materials, and also synthetic fibers, for example, ofregenerated cellulose, or natural materials, for example, cellulose,linen or above all cotton. They are suitable for dyeing by the so-calleddirect dyeing methods and also by printing or foularding dyeing methods,especially from aqueous alkaline solutions, which may contain a highcontent of salts, for example, by the process in which the dyestuff isfixed on the material to be dyed by a heat treatment, for example, bysteaming, in the presence of an alkali, or preferably by storing thedyed or printed material at room-temperature or at a slightly elevatedtemperature, e.g. at a temperature between 15 and 40C for 1 to 24 hoursaccording to the socalled cold-pad-batch-process. Due to the reactivedihalogenopropionylamino substituent a chemical bonding is formedbetween the chromophore of the azo dyestuff and the cellulosic fiberduring the fixation process.

In order to remove non-fixed dyestuff and to improve the properties ofwet fastness of the dyeings so produced on cellulose fibers the dyeingsare thoroughly rinsed with cold and hot water. Advantageously they mayalso be treated with a dilute and advantageously slightly alkalineboiling solution of a nonionic detergent or a dispersing agent for ashort time, for example, 510 minutes.

Dyeings produced on cellulosic fibers with the dyestuffs of thisinvention are usually distinguished by the purity of their tints, bytheir good fastness to light and above all by their excellent fastnessto washing.

The following Examples illustrate the invention, the parts andpercentages being by weight:

EXAMPLE 1 10.44 parts of the dyestuff of the formula are neutralizedwith sodium carbonate in 350 parts of water, and 3.4 parts of sodiumbicarbonate are added. While stirring vigorously, a solution of 4.8parts of 01:3-

dichloropropionyl chloride in 10 parts of toluene is The dyestuff dyescotton greenish yellow tints by the process described in Example 13.

23 When the above dyestuff is acylated with 7.5 parts ofazB-dibromopropionyl chloride instead of 4.8 parts ofazB-dichloropropionyl chloride, a product is obtained which likewisedyes cotton fast greenish yellow tints.

EXAMPLE 2 8.76 parts of the dyestuff of the formula .are neutralizedwith sodium carbonate in 300 parts of I short time the acylation of theamino group is complete. The dyestuff is salted out with 70 parts ofsodium chloride, filtered off and dried in vacuo at to C. The dyestuffobtained in this manner dyes cotton bluish red tints.

When the above dyestuff is acylated with an equiva- 3Q lent amount ofazB-dibromopropionyl chloride instead of azB-dichloropropionyl chloride,a product is obtained which dyes cotton by the method described inExample 11 bluish red tints.

EXAMPLE 3 5.18 parts of the dyestuff of the formula HO NH areneutralized with sodium carbonate in 300 parts of water, and thissolution is mixed at room temperature dropwise with a solution of 10parts of azB-dichloropropionyl chloride in 15 parts of acetone, and bythe simultaneous dropwise addition of aqueous sodium carbonate solutionthe pH value of the solution is maintained between 7 and 8. Aftercomplete acylation of the two amino groups the dyestuff is salted outwith parts of sodium chloride and dried in vacuo at 50 to 60C. Thedyestuff dyes cotton bluish-red tints.

By acylating the aminoazo dyestuffs in Column I witha:B-dichloropropionyl chloride as described in the preceding Examplesfurther dyestuffs are obtained that dye cotton the tints shown in ColumnII.

3 NHCOCH3 NHCOCH CH H l OCH SO H 50 H reddish yellow reddish yellowyellow SO H -continued H035- N N NN- scarlet H0 5- -NH SO H HO 5- -N'-N- -N='N- -NH 3 yellow orange C H S 0 H C O 3 HO NH greenish blackgreenish black By acylating the aminoazodyestuffs of Column l of thefollowing table as described in the preceeding Examples, but with anequivalent amount of azB-dibromos H OH OH H propionylchloride, furtherdyestuffs are obtained that dye cotton the tints shown in Column llscarlet red scarlet -continued I ll OH HO S S O 3 H OH c 3 scarlet N-N-N-N- CH H l t N H 50 3 H HO S CQOH COOH H N NH SO H 2 2 N: c H03 S 3 c:N reddish N/ l I yellow c=c=N- -N N=N-c=c I S O 3 H V H 2 N NH 2 NH 2 QMHQ xiii SO H 3 NH 2 SO H 0H CH3 CH3 N=NO N=N Nl-i Scarlet H035 SO3H so Hbrown 5 0 H C H 3 H0 Ho brown SO H EXAMPLE 4 are neutralized with sodiumcarbonate in 750 parts of 530 rt water. 12 parts by volume of ION-sodiumhydroxide pa 8 of the dyestuff of the formula solution and 120 parts byvolume of a sodium OH Ho chromesalicylate solution (containing 2.8 partsof 65 chromium in 100 parts by volume) are added, and the mixture isrefluxed for 3 hours. After cooling, the solu- N: NH 7 tion of the 1:2-chromium complex so formed is neutralized with hydrochloric acid.

5 The above solution is cooled to 0 to 5C and 40 parts 5 of anhydroussodium acetate are added. While stirring vigorously, 40 parts ofazB-dichloropropionyl chloride are added dropwise at to C withinminutes. After 2 hours the solution is neutralized with sodiumcarbonate, and the dyestuff is salted out with sodium chloride andfiltered off.

The dyestuff dyes cotton reddish grey tints.

The parent dyestuff of the above formulais obtain- 7 able, for example,by coupling diazotized 5-nitro-2-' aminophenol with2-phenylamino-S-hydroxynaphthalene-3z6-disulfonic acid and reducing thenitro' group in the resulting dyestuff to an amino group by means ofsodium hydrosulfide.

the above solution which is then cooled to 0 to 5C, and at thattemperature, while stirring vigorously, a solution of 35 parts ofazB-dichloropropionyl chloride is added dropwise. After 1 hour thesolution is neutralized and the dyestuff is obtained by evaporating thesolution in vacuo.

The dyestuff dyes cotton covered violet tints.

By acylating the metalliferous azo dyestuffs listed in Column I withazB-dichloropropionyl chloride or equivalent amounts ofazB-dibromopropionyl chloride as described in Examples 4 and 5 there areobtained dyestuffs that dye cotton the tints shown in Column II.

3. lz2-chromium complex of the dyestuff OH H o i H N N Y 2 H reddishblue S 03H COQH EXAMPLE 5 43.9 parts of the dyestuff of the formula OHHO NH 2 H0 5 $0 K are neutralized with sodium carbonate in 500 parts ofI water. 12 parts by volume of ION-sodium hydroxide solution and 310parts by volume of a cobalt sulfate solution of 5% strength are added,and the mixture is heated for /2 hour at 75 to 80C. The solution of the1:2-cobalt complex obtained in this manner is allowed to cool and thenadjusted to pH==7.

35 parts of anhydrous sodium acetate are added to EXAMPLE 6 stuff issalted out with sodium chloride, filteredoff and I dried in vacuo at 60to C.

The resulting dyestuff of the formula H0 NHCO O N=N s 05H ('31 ClCHCH-CONH dyes cellulose by the process described in Example 11 red-violettints.

If desired, the coupling can be carried out with advantage in thepresence of sodium acetate or sodium bicarbonate.

The 4-(a:B-dichloropropionylamino 1 -aminobenzene-2-sulfonic acid usedin this Example can be prepared thus:

18.8 parts of l:4-diaminobenzene-Z-sulfonic acid are dissolved in 400parts of water, and then neutralized with sodium carbonate. Whilestirring vigorously, 21 parts of azB-dichloropropionyl chloride areadded dropwise at to 5 in the course of minutes, and at the same timethe reaction solution is neutralized with dilute sodium carbonatesolution so as to maintain the reaction solution at a pH value of 6 to7. On completion of the reaction, the whole is acidified withhydrochloric.

acid, filtered, and the reaction product washed with saturated sodiumchloride solution.

In a similar manner 5-( a:B-dichloropropionylamino)-1-aminobenzene-2-sulfonic acid can be prepared from 5-aminol-aminobenzene-2-sulfonic acid.

In the following Table further dyestuffs are listed which are obtainedaccording to the process described in Example 6 by coupling thediazotized amines listed in column 1 with the coupling components listedin column 2 and which yield on cotton dyeings having the shadesindicated in column 4. In this Table the underlined arnino-group meanseither an ozzB-dichloropropionylamino group (I in column 3) or ana,B-dibromopropionylamino group (II in column 3). The diazo componentscorresponding to the indicated capital letters are the following:

A: aniline B: l-aminobenzene-2-sulfonic acid C:l,3-cliaminobenzene-6-sulfonic acid D: l,4-diamin0benzene-6-sulfonicacid E: 1-amino-4-methylbenzene-6-sulfonic acid F:1-amino-4-methoxybenzene--sulfonic acid G:1-amino-4-chlorobenzene-6-sulfonic acid H:l-amino-4-bromobenzene-6-sulfonic acid J:l,3-diamino-4-chlorobenzene-6-sulfonic acid K:l,3-diamino-4-methoxybenZene-6-sulfonic acid L:l,3-diamino-4-methylbenzene-6-sulfonic acid M:l-amino-4-phenoxybenzene-6-sulfonic acid N:l,4-diarninobenzene-2,S-disulfonic acid 0:l,4-diaminobenzene-2,6-disulfonic acid P:l,3-diaminobenzene-4,6-disulfonic acid Q: l-aminobenzene-2,5-disulfonicacid R: l-aminobenzene-2,4-disulfonic acid S:Z-aminonaphthalene-4,8-disulfonic acid T:l-aminonaphthalene-3,6-disulfonic acid U:2-aminonaphthalene-5,7-disulfonic acid V:2-aminonaphthalene-6,8-disulfonic acid X:2-aminonaphthalene-4,6,8-trisulfonic acid -continued III bluish-red I Ired I H l H l H n H II I I I II l-amino-8-hydroxynaphthalene- I4,6-disulfonic acid bluish-red red 39) l-acetylamino-8-hydro xynaphtha-I lene3,6-disulfonic acid bluish-red red l-N-benzoylamino-8-hydroxynaphthalene3,-disulfonic acid bluishred 45) H H46) 43 I! II I-th lI-ii-iI-t l-N-acetylamino-8-hydroxyrednaphthalene-4,6-disulfonic acid bluish-red red I-N-butyrylamino-8-hydroxynaphthalene-4,6-disulfonic acid 50) 5 l 52) 53)54) l -N-benzoylamin o-S-hydroxynaphthalene-4,6-disulfonic acid 55) 56)57) 58) 59) bluish-red 2-ureido-5-hydroxynaphthalene- 7-sulfonic acidorange reddish-orange II III Y: 2-aminonaphthalene-l-sulfonic acid.

I II III IV 1) A l-amino-8-hydroxynaphthalene I red 3,6-disulfonic acid2) A II 3) B H I H J 2) K 3) L C 5) D 6) J 7) K 8) L2ureido-5-hydroxynaphthalene-7-sulf0nic acid2-(N-a,B-dichloropropionyl-N-methyl)-amino-5-hydroxynaphthalene-7-sulfonic acid reddish-orange orange I I I (I 10 1112) l3) I4) 15) 16) 17 1s 19 20) -continued I ll2-N-a,B-dibromopropionylmethylamino5 -hydroxynaphthalene-lsulfonic acid2-amino-S-hydroxynaphthalene-7-sulfonic acid2-N-a,B-Dichloropropionylamino-S-hydroxynaphthalenc-7-sulfonic acid2-N-a,B-dibromopropionylamino-S-h ydroxynaphthalcne-7-sulfonic acid2-amino-8-hydroxynaphthalenc-6-sulfonic acid2-N-methylaminc-8-hydroxynaphthalenc-6-sulfonic acid 2-cv,B-dichl0ropropionylamino-8-hydroxynaphthalene- 6-sulfonic acid2-N-a,B-dibrompropionylamino-8hydroXynaphtl1alene- 2-(N-a,B-dichloropropionyl-N-methylamino)-8 hydroxynaphthalene--sulfonicacid 2-( N-a,B-dibrompropionyl-N-methylamino)-8-h'droxynaphthalene-6-sulfonic acid l-hydroxyn aphthalin Z-hydroxynaphthalin l-hydroxynaphthalin-4-sulfonic acid III reddish-orange orangeI I reddish-orange orange reddish-orange orange reddish-orange II orangercddish-orange II orange-red red orange red scarlet reddish-orange redscarlet reddish-orange red scarlet reddish-orange red scarlet yelloworange II red orange II 2-aminonaphlhaicnc-7-sulfonic acid2-aminonaphthalene-8-su1fonic acid i-arninonaphthalcnc4 su1fonic acid laminonaphthaicnc-5-su1fonic acid l-aminonaphtha1enc-6-sulfonic acidl-aminonaphthalcnc-7-sulfonic acid l-aminonaphthalene-8-sulfonic acid2-aminonaphthalcnc-S-sulfonic acid 2-aminonaphthalcnc-6-sulf0nic acid2-aminonaphthalenc-7-su1fonic acid Z-arninonaphthalenc 8-sulfonic acid laminonaphthalenc-4-sulfonic acid 1-aminonaphthalenc-5-su1fonic acid1-aminonaphthalcne-6sulfonic acid 1-aminonaphtha1enc-7-sulfonic acidl-aminonaphthalcnc-8-sulfonic acid 2-aminonaphthalene-5-sulfonic acid2-aminonaphtha1cnc-6-su1fonic acid Z-aminonaphthalcnc 7-sulfonic acid2-aminonaphthalene8sulf0nic acid l-aminonaphthaicnc-4-su1f0nic acid1-aminonaphthalene-5-sulfonic acid l-aminonaphthalene-6-sulfonic acid 1aminonaphthalcnc-7-sulfonic acid 1aminonaphthalcnc-8-su1fonic acidZ-aminonaphthalcne-5-sulfonic acid 2-aminonaphthalcnc-6-sulf0nic acid2-aminonaphthalenc-7-sulf0nic acid 2-aminonaphthalenc-8-sulfonic acidl-aminonaphlha1cnc-4-sulfonic acid 1-aminonaphthalenc-5-sulfonic acid1-aminonaphthaicne-6-sulfonic acid 1-aminonaphthalenc-7-sulfonic acidl-aminonaphthalene-8-sulfonic acid Z-aminonaphthalene-S-sulfonic acidLaminonaphthalene-6-su1fonic acid 2-aminonaphthalene-7-su1fonic acid2-aminonaphthalene-8-su1fonic acid l-aminonaphthalcnc-4sulfonic acidl-aminonaphthalene-5'sulfonic acid l-aminonaphtha1ene-6-su1fonic acidl-aminonaphtha1ene-7-sulfonic acid 1-aminonaphtha1enc-8-su1fonic acid2-aminonaphtha1ene-5-su1fonic acid 2-aminonaphthalene-6-su1fonic acidLaminonaphthalene-7-sulf0nic acid 2-aminonaphtha1enc-8-sulfonic acid 1aminonaphtha1enc-4-sulfonic acid 1-aminonaphthalene-5-sulfonic acid1-aminonaphthalenc-6-sulfonic acid 1-aminonaphthalcnc-7-sulfonic acidl-aminonaphthalene-8-sulfonic acid Z-aminonaphthalcnc-5-su1fonic acid2-aminonaphthalene-6-su1fonic acid 2-aminonaphtha1cne-7-su1fonic acid2-aminonaphthalcne-8-sulfonic acid l-aminonaphthaicne-4-sulfonic acid1-aminonaphtha1ene-5-sulfonic acid 1-aminonaphtha1en'e-6-su1fonic acid1-aminonaphthalcnc-7-su1fonic acid 1-aminonaphthalene-8-sulfonic acid1-hydroxynaphthalene-4-su1fonic acid 1-hydroxynaphthaiene-Ssulfonic acid2-hydroxynaphthalcne--sulfonic acid 2-hydroxynaphthalcnc-7-sulfonic acid2-hydroxynaphthalenc-S-sulfonic acid 1-hydroxynaphthalcnc-4-sulfonicacid 1-hydroxynaphthalenc-5-sulf0nic acid2-hydroxynaphthalene-6-su1fonic acid 2-hydroxynaphthaiene-7-su1fonicacid 2-hydroxynaphthalene-8-su1fonic acid1-hydroxynaphthalenc-4-su1fonic acid l-hydroxynaphthalcnc-S-sulfonicacid Z-hydroxynaphthalcne-o-sulfonic acidZ-hydroxynaphthalcnc-7-su1fonic acid 2-hydroxynaphthalenc-8-sulf0nicacid 1-hydroxynaphthalene-4-sulfonic acid1-hydroxynaphtha1enc-S-sulfonic acid Z-hydroxynaphthalene-6-suif0nicacid Z-hydroxynaphthalene-7-sulfonic acidZ-hydroxynaphthalene-8-sulfonic acid 1-hydroxynaphthalene-4-sulfonicacid 1-hydroxynaphthalene-S-sillfonic acid1-hydroxynaphthalene-G-sulfonic acid Z-hydroxynaphthalcnc-7-sulfonicacid Z-hydroxynaphthalene-8-sulfonic acidl-hydroxynaphthalene-4-sulfonic acid l-hydroxynaphthalene-S-suifonicacid 2hydroxynaphthalenc-6 su1fonic acid 2-hydroxynaphthalenc-7-sulfonicacid Z-hydroxynaphthalene-8-su1fonic acidl-hydroxynaphthalcnc-4-sulfonic acid 1-hydroxynaphthalene-S-sulfonicacid Z-hydroxynaphthalcne-6-suifonic acid2-hydroxynaphthaiene-7-sulfonic acid -continued orange I I orange 1 1 1orange 7 11 orange I!

1. A DISAZO DYESTUFF OF THE FORMULA
 2. The disazo dyestuff as claimed inclaim 1 of the formula
 3. The disazo dyestuff as claimed in claim 1 ofthe formula
 4. The disazo dyestuff of the formula
 5. The disazo dyestuffof the formula